Manufacture of sulfur dyestuffs



Patented N... 19, 1929 PATENT OFFICE HERMANN PLAUSON, F HAMBURG, GERMANYMANUFACTURE OF SULFUR DYESTUFFS No Drawing. Original application filedJune 28, 1924, Serial No. 722,954 and in Germany July 2, 1923. Dividedand this application filed January 13, 1921' Serial No. 161,019.

This invention relates to the manufacture of dark or black dyescontaining sulfur and is a divisional application on my copendingapplication Serial No. 7 22,954, filed June One of the objects of theinvention is the production of a dye direct from acarbonaceous materialby the action of sulfur in conjunction with a substance of an alkalinena- 10 ture or having an alkaline reaction. Other objects of theinvention are the production of black brownish-black or brownish-yellowsulfur dyes directly from such raw materials as bitumen, pitches, soots,peat and the like and also earthy coals, lignite, cannel coal, pitchcoal, anthracite and lampblack. materials are subjected to a sulfurizingprocess by heating with sulfur and a substance of an alkaline nature orhaving an alkaline reaction such-as sodium sulfid, sodium hydrate,sodium carbonate, or the like. According to one feature of the inventionthe carbonaceous material is heated with sulfur together with the alkalisubstance but the material may also first be fused with sulfur andafterwards treated with the alkali substance.

' The material may also be heated with a preformed polysulfid melt.

The raw material may be subjected to a prtreatment as describedhereafter; Other features of the invention will be apparent from thefollowing description and examples.

In the following process the entire: coal is preferably converted into afinely dispersed state. The process depends upon the phenomenon thatpowdered materials ofthe kind referred to such as lignite or pitch coalby melting in an admixture with sulfur alone or with polysulfides give acolloidal product like a sulfur dye and the process is illustrated bythe folowing examples.

Ewample 1 In a direct heated kettle which is best formed of Spencermetal 1000 grams of sodi-' 5 gins at about 110 C. According to the tem-The raw produced.

perature at which the process is worked, dyestuffs are obtained ofdifferent tints. If the reaction is allowed to go for example at 200 C.there is formed a dye stuff which gives cotton a light brown tone. Adark brown black is obtained if the temperature rises to 300. If a finaltemperature of 300 to 310 is employed there results on cooling a drycrumbly black powder which gives with water a colloidal dye bath withwhich cotton can be directly dyed black. The purification of the dyestuff is possible by the known methods of precipitating with acids orsalts, etc., but is not however, necessary. In the dyeing process Turkeyred oil can be added by which means a warm brown or black is 0'. Example2 1000 parts of sodium sulfid and 600 parts of sulfur are mouldedtogether at 100 to 110 C.

then 500 grams of lignite are added slowly a little at a time thereto,and heated with stirtained an ash grey crumbly mass which is solubleafter grinding.

Example 3 A black dye for the oil and printing trade can be obtainedwithout the application of sodium sulfid by the following method. 500parts of powdered lignite are stirred up with 500 parts of concentratedsulfuric acid. To this are added 750 parts of sulfur, and the mass thenheated in the absence of air to 130 to 150. There is formed thereby adry mass with the evolution of sulfur dioxid which when cold can be wellproduced. Bywasing with boiling. weakly alkaline Water, a good black dyeis obtained which can be used as a substitute for the finest lamp black.If sodium sulfid is added to the substances, the mass can be convertedto the soluble state by further heating at 300. Instead of lignite allkinds of cannel 'coal or similar pitch coal can be employed.

' Example 4 ring to 300 to 310 C. There is thereby obdried preferablyunder vacuum.

finds application in the textile industry or as a filling material forplastic masses, for staining, or the manufacture of boot polish. Insteadof clay other neutral earths such as ochre can be used. They must,however, always be present in a highly dispersed state or must beconverted by the known method into the colloidal form for theirapplication.

Emample 5 100 parts of crude bitumen from lignite are reacted upon by240 parts of sodium sulfid and 100 parts of sulfur according toExample 1. -After heating for 3 to 5 hours at 200 to 250 the mass isallowed to cool and A dark brown dye stuff result-s. If the bitumen istreated with concentrated or preferably with fuming sulfuric acid andafterwards the sulfonated product treated by the before describedpolysulfid melt, a deep black dye stuff is obtained.

Useful results may be. obtained by pretreatment with sulfur chlorid. Ifthe bitumen is treated with a sulfuric acid saltpeter mixture, abrown-black tone is produced, Whereas by previous treatment withchlorine a dark green results. Instead of bitumen, lignite or pitchcoalof all kinds can be treated by a sulfonation, nitration orchlorination process. The relative amount of resulting product and theoperating temperature can be altered according to the shade desired. For the purpose of producing different tints a small addition ofcompounds of an organic or inorganic nature can be made, for example,the phenols and their derivatives, aniline or its derivatives, orhomologues, bcnzidine, chlor-di-nitro-benzene, naphthalene, indophenol,urea etc.

100 grams of sodium sulfid, 400 grams of sulfur and 500 grams of Englishanthracite finely powdered are well mixed in a kettle and heated slowly,with stirring to 300 to 350 C. After cooling there results a blackpowder which gives a colloidal solution in water and possesses theproperty of dyeing cotton or artificial silk a beautiful brown black. Asstarting product, German orother anthracite may be employed. If theamount of sulfur and sodium sulfid in the melt and the time of heatingbe increased, a substantially black dye is produced. Similar productsare also obtained if an addition of copper salts or chromium compoundsto a small amount was made to the melt.

The proportionual amounts of sodium sulfid sulfur and coal can bealtered according to the desired dyeing effect. The processcan naturallybe carried out according to the previous examples.

Example '1 1250 parts of sodium sulfid, 500 parts of sulfur, 500 partsof charcoal dust are treated according to example 1 at a temperature of300 to 350 C. If on account of overheating a modification insoluble inwater is produced, this is converted into the soluble state by theaddition of sodium sulfid.

Ewamplc 8 500 parts of lamp black, 1250 parts of sodium sulfid, and 500parts of sulfur are treated as in Examples 7 or 8, at a temperature of300 to 400 C. or at most 450. A substantially bitumen-free lamp blackgives a black colloid. The pure lamp black may be mixed with 3 to 10parts or more of the bituminous extraction production of anthracite,pitch coal or such like charcoal or pitch products, and if thesemixtures are acted upon by the po ysulfid melt, a fast dye results.

In the preceding examples sodium sulfid has always been employed. Now ithas been found that the sodium sulfid is not absolutely necessary, butcan be replaced by other alkalis, e. g. caustic alkali or alkali metalcarbonate.

This way of proceeding is not obvious since sodium hydrate andespecially sodium carbonate only react very slowly with sulfur and itwas not known that coal is altered by such a mixture. Experiment hasshown that a sulfur melt by the action of sodium hydroxide or carbonatefurnishes directly a dyestuff. If a good result is required it isadvantageous to increase the sulfur content above that indicated in theprevious examples.

Example .9

date and sulfur can be altered in both direc-- tions according to theshade of dye desired. Instead of sodium hydroxide other alkali metalhydroxides can be employed. Obviousthemelt can be carriedthrough bytheother methods of working shown in the previous examples.

The same result is reached if instead of lignite, cannel coal, turbaniteor other bituminous coal is employed. A good black dye is obtained whicheasily dyes cotton and artificial silk.

E wample 10 500 grams of finely pulverized English anthracite, 820 gramssulfur and 1000 grams of caustic soda are subjected to a melt as inExample 1 at a temperature of 300-350". After cooling and powdering, adark brown dyestuff is obtained. When heated for a longer time to 350470the product takes on a dark black tone. The solubility in this case isfurther improved by further addition of alkali metal sulfid. The dyeingcan be carried out according to Example 10 with or without addition offixing materials or of dye improvers.

E mample 11 1000 parts of caustic soda, 850 parts of sulfur and 500parts of charcoal or pitch coal, produced at the lowest possibletemperature, are formed into a melt and then slowly heated from350-450". The mass can, after cooling, be ground to a fine powder whichon the addition of sodium sulfid can be completely brought intosolution. In a similar manner different lamp blacks can also be used forthe production of dyestuffs.

E wample 12 106 parts of calcined soda, 80 parts of sulfur and 40 toparts of lignite are heated under continual stirring to 300350. Thereaction goes slowly and almost imperceptibly and finally a yellowVapour is evolved and the usual deflagration takes place as isfrequently to be observed in the production of sulfur dyes. A deep blackpowder is formed whose solution gives cot-ton or artificial silk a warmdark brown tone. By longer melting at the above mentioned temperature orby the addition of small amounts of inorganic or organic compounds astoning agents to the melt or to the dyebath, a black dye shade can beobtained. Instead of calcined soda, crystallized sodium carbonate in acorresponding amount can be used. Other carbonates are also applicable;the best result is given, however, by sodium carbonate.

All the other examples may be carried out with alkali metal carbonateinstead of hydroxide. if mineral coals are used as starting materials.In the using of crystalline soda it has shown itself to be profitable tocarry out the melt in an autoclave, for instance, under pressure; thereis obtained in this way a particularly homogeneous end product.Naturally the process can take place with reflux condensation of thewater of crystallization.

It has also been found that it is possible to simplify the production'ofsulfur dyestuffs from mineral coal or the like carbonaceous material ifthe sulfur-alkali, melt is not applied directly to the mixedconstituents, but

coal and sulfur are first heated together and then directly, after orbefore cooling and powdering, the product of the melt is subjectedto'the action of a further melting with the addition of the necessaryamount of caustic alkali or alkali metal sulfid. The dyestuffs obtainedin this way gives a considerably deeper black, and the action of thealkali melt is more complete and simple as the frothing and similarundesirable phenomena are eliminated from the process.

E wample 13 400 grams of lignite or the like bituminous coal is heatedwith 800 grams sulfur to 120150 C., preferably in the absence-of air for10 to 30 minutes. After this time the melt can be cooled and thenpulverized or directly treated further by heating with 800-1000 gramscaustic soda, preferably in absence of air to 300400 C. until ahomogeneous melt results, There is obtained a very good dye of deepblack tone. Instead of caustic alkali a suitable amount of alkali metalsulfid such as sodium sulfid, can be taken. In the latter case themelting process can be carried out at 250-300 C. in an autoclave underpressure preferably obtained by the use of a neutral gas. By theemployment of alkali metal sulfid containing water of crystallization,the melt can be undertaken also under a reflux condenser. The processesof the preceding examples can be carried out in a similar manner.

It has further been observed that it is advantageous in the melting withsulfur to add compounds of copper, iron, zinc, nickel, cobalt, tin orchromium, or the metals themselves inthe powder form in amounts of 15%as thereby the dyes possess an especially full tone. In similar mannersmall amounts of organic compounds suitable for altering the shades ofthe dyes can be added and the melting process undertaken.

All the dyes made according to the process of the preceding examplesgive brown to black dyeings on mercerized cotton or on artificial silk;on crude and non-mercerized cotton a brown-black tone can at best beproduced or a very high concentration of the dyebath. or long boiling,etc., must be employed.

It has also been found that dyes which produce a deep black on differentmaterials can be obtained, if the impure constituents are removed fromthe crude coal before the polysulfid melt in the dye synthesis. I Withthis object the coal is treated in a pressure autoclave or in a colloidmill or similarly acting apparatus with alkali and water and freed byfiltering 0r settling from the valueless materials. The suspendedmaterial is then precipitated with a weak gaseous acid such as carbondioxid, sulfur dioxid, or by a dilute acid such as hydrochloric,sulfuric, nitric acid or the like. There is obtained in this 111311119.as starting material for the dye manufacture a purified and more or lessopened up preparation.

This product is dried and can be used directly for the production ofsulfur dyestuffs according to the processes of the previous examples. Incertain cases it can be subjected with advantage, even in the moiststate to a process of sulfonation, oxidation, chlorination, nitration,azotization or reduction according to the tint desired, or even toseveral of the above substitution processes in any suitable order. Theproduct obtained by extracting coal such as crude bitumen, pitch bitumenand the like with organic solvents, can be treated in similar manner.The characteristic feature of this part of the process consists in thefact that the starting materials for the manufacture of the dyestuff,obtained by the above described method of purification or extraction arealways produced without the application of dry distillation. Only thesegive, in fact the desired deep black dyes as resulting products whilethose obtained through the distillation of carbonaceous materials are ofno value as they almost always sufi'er deep seated changes.

If the product obtained from coal by the above method is subjected tothe polysulfid melt, a deep black dyestufi' is obtained which isabsorbed by cotton much better than the substance produced by the directprocess from coal.

Example 1.4

fuging or filtration, the residue freed from soluble salt by washingwith water and then dried or subjected in the known way to asulfonation, nitration, chlorination, azotization or a. reductionprocess. The dry product obtained from this process or from the knownchemical operations is converted into a sulfur dyestulf in the mannerdescribed in the previous examples. Black dies are obtained by thechlorination or sulfonation or the like,

according to the manner of the substituents.

introduced, of different shades.

The material may be previously purified or separated into component byany'method, for example by treatment in a high speed me chanicaldisintegrator such as a colloid mill. The coal may be previously heatedeither alone or with any known chemical or it may be partiallydistilled.

Example 15 If the bitumen has been obtained according to a known processby extraction with hydrocarbons, the residue is worked as in Example 14.The product obtained by this opening up process is added to the bitumenobtained from the extraction process before the further treatment by theknown process by extraction with hydrocarbons, the residue is worked asin Example 14; The product obtained by this opening up process is addedto the bitumen obtained from the extraction process before the furthertreatment by the melting process or by a solution process.

The working of the product obtained from Examples 14 or 15, can alwaysbe carried out in two ways. Either it can be subjected directly to apolysulfid melt or first by a known method to sulfonation, chlorination,nitration, or other conversion processes customary in the production oforganic dyes, such as nitrification (azotierung) condensation and thelike, and these products can then be converted by a melt with alkali andsulfur to the dyestufi'. The result in both cases is a dyestuff whichproduces on the material a black-green tone, whereby if necessary, thechlorinationor nitration or the like which has been accomplished makes anoticeable difference in the shade of the pure product, which can alsobe influenced in this way if desired.

For the improvement of the tint of the dye taken up, small amounts oforganic compounds can be employed which give dyes in the polysulfid meltwhich are suitable for altering as desired, the shade of the finalproduct towards green-black or blue-black. Naturally the choice of thesewill be governed by all previously gathered experience on the action ofthe order of substitution on the shade. Such compounds, for example, aspara-nitroso-phenol and para-amidephenol', paradihydroxybenzen'e, andmoreover dinitraniline, dinitrophenol and the like are suitable. Forobtaining bluer tints, naphthalene derivatives, for example, substitutedin the peri-position are employed with success. Halogen-indophenolsalter the shade towards the green indophenols chlorinated in the nucleustowards the green-blue and unchlorinated indophenols towards the pureblue.

In the appended claims by semicarbonized carbonaceous material, I meanmaterial which by a natural process or by a heat treatment has beendecomposed to yield a residue consisting of carbon more or less looselychemically bound with other substances and which may be a solid orliquid or semi-liquid mass.

The term coal substance comprises all coals, lignite and solid orsemi-liquid carbonaceous products derived therefrom.

I declare that what I claim is 1. Process for the production of a dye inwhich a semi-carbonized carbonaceous material is pretreated with amineral acid and is thenheated with a sulfur and afterwards with aninorganic alkaline substance.

' 2. Process for the production of a dye in which a coal substance ispretreated with a mineral acid and then is heated with sulfur, andafterwards with an inorganic alkalin substance.

3. Process for the productionof a dye in which lignite is pretreatedwith a mineral acid and then is heated with sulfur, and afterwards withan'inorganic alkaline substance.

4. Proces for the production of a dye in which a semi-carbonizedcarbonaceous material is pretreated with strong sulfuric acid, and isthen heated with sulfur and with an inorganic alkaline substance.

5. Process for the production of dyes in which a semi-carbonizedcarbonaceous material is pretreated with a mineral acid and then isheated with sulfur, with an inorganic I alkaline substance and withwater under pressure.

In witness whereof, I have hereunto signed my name this 3rd day ofJanuary, 1927.

HERMANN PLAUSON.

